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1Health significance of drinking water calcium and magnesiumFrantišek Kožíšek,
M.D., Ph.D.National Institute of Public HealthFebruary 2003IntroductionDrinking
water quality is currently defined only as the absence or a strictly limited
presence of certain undesirable substances, however, distilled or demineralized
water can hardly be considered as an ideal of good drinking water. Drinking
water is a complex system of mineral substances and gases dissolved in water.
Calcium (Ca) and magnesium (Mg) are among the important and most thoroughly
studied natural water constituents.The present contribution summarizes the
existing knowledge of health significance of drinking water Ca and Mg and the
attempts to reflect it in regulation and suggests how to bridge the regulatory
gaps in this field.Calcium, magnesium and water hardnessIf we want to work on
calcium and magnesium in drinking water, a third parameter is to be taken into
account: water hardness, even if this term is incorrect and obsolete from a
strictly chemical point of view. That is to say that both of these elements
largely have not been analysed individually in drinking water in the past, but
just non-specifically in summary as hardness. This approach was applied in many
studies focused on health effects of this “water factor”.Since the definition of
water hardness is approached either analytically or technologically, it was not
and still has not been defined in a unified manner, and as with other
parameters, multiple definitions have been available and multiple units have
been used to express it (German, French, and English degrees; equivalent CaCO3or
CaO in mg/l). Initially, water hardness was understood to be a measure of the
capacity of water to precipitate soap, which is in practice the sum of
concentrations of all polyvalent cations present in water (Ca, Mg, Sr, Ba, Fe,
Al, Mn, etc.); nevertheless, since the other ions (apart from Ca and Mg) play a
minor role in this regard, later it has been generally accepted that hardness is
defined as the sum of the Ca and Mg concentrations, determined by the EDTA
titrimetric method, and expressed in mmol/l (ISO, 1984) or as CaCO3equivalent in
mg/l (Standard Methods, 1998), less frequently as the CaO equivalent.From the
technical point of view, multiple different scales of water hardness were
suggested (e.g. very soft – soft – medium hard – hard – very hard). Expectedly,
both extreme degrees (i.e. very soft and very hard) are considered as
undesirable concordantly from the technical and health points of view, but the
optimum Ca and Mg water levels are not easy to determine since the health
requirements may not coincide with the technical ones.Calcium and magnesium
presence in watersWater calcium and magnesium result from decomposition of
calcium and magnesium aluminosilicates and, at higher concentrations, from
dissolution of limestone, magnesium limestone, magnesite, gypsum and other
minerals. Anthropogenenic contamination of drinking water sources with calcium
and magnesium is not common but drinking water may
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2be intentionally supplemented with these elements while treated, as happens
with deacidification of underground waters by means of calcium hydroxide or
filtration through different compounds counteracting acidity such as CaCO3,
MgCO3and MgO, and possibly also with stabilization of low-mineralized waters by
addition of CaO and CO2.In low- and medium-mineralized underground and surface
waters (as drinking waters are), calcium and magnesium are mainly present as
simple ions Ca2+and Mg2+, the Ca levels varying from tens to hundreds of mg/l
and the Mg concentrations varying from units to tens of mg/l.Magnesium is
usually less abundant in waters than calcium, which is easy to understand since
magnesium is found in the Earth’s crust in much lower amounts as compared with
calcium. In common underground and surface waters the weight concentration of Ca
is usually several times higher compared to that of Mg, the Ca to Mg ratio
reaching up to 10. Nevertheless, a common Ca to Mg ratio is about 4, which
corresponds to a substance ratio of 2.4 (Pitter, 1999).Physiological role of
calcium and magnesium in the human body Both of these elements are essential for
the human body. Calcium is part of bones and teeth. In addition, it plays a role
in neuromuscular excitability (decreases it), good function of the conducting
myocardial system, heart and muscle contractility, intracellular information
transmission and blood coagulability. Osteoporosis and osteomalacia are the most
common manifestations of calcium deficiency; a less common but proved disorder
attributable to Ca deficiency is hypertension. Based on newly acquired
epidemiological data, implication of Ca deficiency in other disorders is
currently being discussed. The recommended Ca daily intakefor adults ranges
between 700 and 1000 mg (Scientific Committee for Food, 1993; Committee on
Dietary Reference Intake, 1997). Some population groups may need a higher
intake.Magnesium plays an important role as a cofactor and activator of more
than 300 enzymatic reactions including glycolysis, ATP metabolism, transport of
elements such as Na, K and Ca through membranes, synthesis of proteins and
nucleic acids, neuromuscular excitability and muscle contraction etc. It acts as
a natural antagonist of calcium. Magnesium deficiency increases risk to humans
of developing various pathological conditions such as vasoconstrictions,
hypertension, cardiac arrhythmia, atherosclerotic vascular disease, acute
myocardial infarction, eclampsia in pregnant women, possibly diabetes mellitus
of type II and osteoporosis (Rude, 1998; Innerarity, 2000; Saris et al, 2000).
These relationships reported in multiple clinical and epidemiological studies
have recently been more and more supported by the results of many experimental
studies on animals (Sherer et al, 2001). The recommended magnesium daily intake
for an adult is about 300-400 mg (Scientific Committee for Food, 1993; Committee
on Dietary Reference Intake, 1997). Beginnings of research into health
significance of water hardnessThat drinking water is also an important source of
essential (i.e. essential to life) elements such as Ca and Mg was already known
before world war II (Kabrhel, 1927; Widdowson, 1944). The significance of
drinking water calcium for nutrition was underlined in the 1940’s by a German
nutritionist R.Hauschka who recommended sodium hydrogen sulphate to be added to
water prior to boiling in order to maintain the level of dissolved calcium and
to prevent loss of calcium due to precipitation (Hauschka, 1951).
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3Health significance of water hardness was directly evidenced in the late
1950’s. The relationship between water hardness and the incidence of vascular
diseases was first described by a Japanese chemist Kobayashi (Kobayashi, 1957)
who showed, based on epidemiological analysis, higher mortality rates from
cerebrovascular diseases (stroke) in the areas of Japanese rivers with more acid
(i.e. softer) water compared to those with more alkaline (i.e. harder) water
used for drinking purposes.Several studies followed and most of them confirmed
an inverse correlation between water hardness and mortality from cardiovascular
diseases (CVD). Among the best known studies were those by H.A.Schroeder who
demonstrated, among others, correlation between mortality from CVD in males aged
45-64 years and water hardness in 163 largest cities of the USA (Schroeder,
1960) and summarized his results using the following compelling dictum: „soft
water, hard arteries“. Other studies were published by Morris in Wales (Morris
et al, 1961) and Canadian, Finnish, Italian, Swedish and other authors. A review
of most relevant papers of the 1960’s is given e.g. in a WHO Bulletin (Masironi
et al, 1972) or by Sharrett and Feinleib (Sharrett et al, 1975).An interesting
British study (Crawford et al, 1971) focused on variation in mortality from CVD
depending on water hardness in 11 British cities between 1950 and 1960. Water
hardness increased in five cities and decreased in six cities. Within the given
period mortality from CVD in the UK increased by 10% on average compared to 20%
in the cities supplied with softer water than before and compared to 8,5% only
in the cities supplied with harder water than before.It is interesting to note
that significant differences in cardiovascular pathology and the magnesium
content of the cardiac muscle were found between males who had died from
infarction and those who had been victims of traffic accidents and between those
living in the areas with soft or hard water: harder water was associated with a
higher magnesium content of the cardiac muscle (Crawford et al, 1967; Anderson
et al, 1973; Neri et al, 1975; and six other studies given in Rubenowitz et al,
1999). Correlation between the water Mg level of and the Mg content of skeletal
muscles is also described in a Swedish study of the late 1980‘s (Landin et al,
1989).Within the first two decades of research into water hardness in
association with CVD more than 100 papers were published (Hewitt et al,
1980).From the very beginning the crucial question was what the „unknown water
factor“ responsible for the positive/negative effect on CVD morbidity was. Apart
from the calcium and magnesium content alone as the major factor implicated in
water hardness and possibly the Ca to Mg ratio, a role played by other trace
elements both beneficial to health (Li, Zn, Co, Cu, Sn, Mn, Cr ...) and toxic
(Pb, Cd, Hg) was considered; nevertheless, no significant correlation between
the content of any of these elements in water and CVD morbidity was found or
repeatedly confirmed in other studies. Attention was paid not only to the theory
of the content of these elements at source but also to higher corrosive
potential of soft water that can support higher leakage of toxic compounds from
the water pipe network.Over the years, evidence has accumulated that magnesium
is the major beneficial agent involved, while calcium has only a supportive
effect against CVD (Eisenberg, 1992). Although only two out of three studies
have shown correlation between cardiovascular
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4mortality and water hardness, the studies carried out on the water magnesium
alone have practically all shown an inverse correlation between cardiovascular
mortality and water magnesium level (Durlach et al, 1985).In the late 1970’s,
the issue of an optimum composition of drinking water, particularly if obtained
by desalination, was in the centre of attention of the WHO. The WHO also
emphasized the importance of mineral composition of drinking water and warned
e.g. against the use of cation exchange sodium cycle softening in water
treatment (WHO, 1978; WHO, 1979). An international group of experts who met in
1975 under the auspicies of the European Commission also concluded: „although it
has not yet been possible to establish any relationship between the cause and
effect, the existence on an association between water hardness and mortality
cannot be dismissed“ (Amavis et al, 1976).The 1980’s and criticisms of the
existing epidemiological studiesIn the 1980’s the wave of interest in the effect
of water hardness on CVD morbidity rather subsided; it seemed that any new
insight into the issue could not be expected. The focus was on confirming the
role of magnesium as a crucial factor of hardness and on first attempts of more
general quantification of its protective effect (see below).What made a new
challenge to publication of further studies in the 1990’s were criticisms of the
existing studies (e.g. Comstock, 1980). Such criticisms were partly justified
since based on new epidemiological methods: they revealed methodical drawbacks
of the previous studies that were mostly ecologic. This means that they
evaluated morbidity at a population group-based level rather than at an
individual-based level and did not establish individual exposure to calcium and
magnesium from water. Some of the studies did not even analyse water for the
calcium and magnesium content, but focused on water hardness only, and
consequently, did not allow to specify the implication of either calcium or
magnesium. In other studies, the confounders possibly involved in CVD morbidity
such as age, socio-economic factors, alcohol consumption, eating habits,
climatic conditions etc. were not adequately taken into account. Nevertheless,
most studies dealing with individual exposure confirmed an inverse correlation
between the drinking water Mg level and the risk to population of developing CVD
as described in ecologic studies, e.g. a vast Finnish cohort study (Punsar et
al, 1979), a case-control study carried out in the same country (Luoma et al,
1983), an American study (Zeighami et al, 1985) and a USSR study (Novikov et al,
1983).The criticisms also pointed out that not all studies then had found
correlation between water hardness and CVD morbidity. This is less compelling
since water hardness is only one - and probably not the crucial one – of
multiple factors possibly involved in CVD morbidity. If other factors which are
not taken into account prevail, the effect of water hardness may be biased. In
some cases, such „failures“ to document water hardness effect were
retrospectively explained by a low level of crucial magnesium in hard water and
subsequent insignificant difference in the Mg content between soft and hard
water (Bar-Dayan et al, 1997). Such explanation seems to be also applicable to
the results of a Norvegian ecologic study (Flaten et al, 1991) showing even a
slightly positive correlation between the magnesium content of drinking water
and CVD morbidity, but all the areas studied had extremely soft water containing
less than 2 mg Mg/l.
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5These criticisms seem to be at the origin of the WHO position adopted with
respect to the last Guidelines for drinking water quality elaborated in
1990-1993. In spite of former enthusiastic opinion of the WHO on water hardness
importance, the Guidelines cautiously admitted some weak relationships between
hardness and health, but concluded: “the available data are inadequate to permit
the conclusion that association is causal. No health-based guideline value for
water hardness is proposed”. Only sensorial and technical disadvantages of
extremely hard and extremely soft water were specified (WHO, 1993). Nonetheless,
some studies on water hardness published in the 1980’s are referred to in the
2ndvolume of the Guidelines (WHO, 1996); surprisingly, some less important or
methodically less developed studies (e.g. Kubis, 1985) are listed among the
references rather than other studies of highest epidemiological significance.The
had a mortality rate from AMI by 35% lower as compared with the consumers of
soft water (< 3,5 mg Mg/l). Any correlation with the water Ca content was not
reported (Rubenowitz et al, 1996).Another study of the same type and by the same
authors focused on correlation between the drinking water Mg and Ca levels and
morbidity and mortality from AMI in 823 males and females aged 50-74 years in 18
Swedish districts, who had developed AMI between October 1, 1994 and June 30,
1996 (Rubenowitz et al, 2000). The study took into account both
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6individual exposure to Ca and Mg from water and food and other known risk
factors for AMI likely to bias the correlation, if any. Although for calcium the
correlation with AMI was not confirmed, magnesium proved to reduce the risk
level by 7.6 % in the group of the quartile with the highest water Mg level (≥
8,3 mg/l) compared to groups exposed to water containing lower levels of
magnesium. Although the total AMI rates were similar in all four groups, the
persons enrolled in the group with the highest water Mg level had a risk level
of death from AMI by a third lower (odds ratio 0.64) as compared to the groups
consuming water containing less Mg than 8.3 mg/l. Multivariate analyses showed
that the correlation found is not caused by other known risk factors. This
finding supports the hypothesis that magnesium prevents primarily sudden death
from AMI, rather than all ischemic heart disease deaths or the risk of suffering
an AMI.Another ecologic Swedish study analyzing causes of a marked difference in
anti CVD drugs consumption between two districts found the difference in water
hardness to be one of possible causes in this regard (Oreberg et al, 1992).
Another ecologic study from seven Central Swedish districts ascribes higher
mortality rates from IHD (by 41%) and from stroke (by 14 %) to water softness
(Nerbrand et al, 1992).In contrast to this series of Swedish studies confirming
the correlation mentioned above, another Swedish study surprisingly concluded
that in cold areas in Sweden, the climate (more precisely the so-called cold
index) has a higher effect on mortality from CVD than water hardness (Gyllerup
et al, 1991). An ecologic study of Tennessee (Erb, 1997) found mortality from
CVD to be by 19% lower in the areas supplied with hard water (161 mg CaCO3/l)
compared to soft water (39 mg CaCO3/l). Even more compelling were the
conclusions of an extensive study (a total of 3013 cases of 1973-1983) carried
out in the former German Democratic Republic: in an area supplied with very hard
water (Mg content close to 30 mg/l) the incidence rate of AMI was 20.6 per 10000
population while in the areas supplied with soft water (Mg content about 3 mg/l)
the rate was as high as 32.7; the difference was even higher in younger age
categories (Teitge, 1990). A Serbian environmental study (Maksimovic et al,
1998) also found out a marked difference in mortality from CVD between the
population groups supplied with drinking water with a „low“ Mg level (less than
20 mg/l) and a high Mg level (52 to 68 mg/l).The difference in the drinking
water Mg level as the most probable explanation for different rates of
myocardial calcifications in persons who died from AMI is reported by authors of
a study carried out in Salt Lake City and Washington D.C. (Bloom et al, 1989).
The significance of a low drinking water magnesium level as a risk factor for
CVD particularly in males is underlined by Rylander’s review article (Rylander,
1996). Multiple past and recent epidemiological studies reported lower rates of
sudden deaths from CVD (including sudden deaths in infants) in the areas with
harder water (Crawford et al, 1972; Anderson et al, 1975; Eisenberg, 1992;
Bernardi et al, 1995; Garzon et al, 1998). It is hypothesized that magnesium
deficiency is implicated in cardiovascular spasms and cardiac arrhythmias
leading to death. Only a statistically slightly significant link between water
hardness and geographical differences in mortality from cerebrovascular diseases
was revealed in a study of North Dakota (Dzik, 1989); similar findings were
reported by a French environmental study not
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7only for cerebrovascular diseases but also for IHD (Sauvant et al, 2000);
nevertheless, water hardness was taken as a general factor regardless of Ca to
Mg levels. While health effects of most chemicals commonly found in drinking
water manifest themselves after a long exposure only, the effects of calcium and
in particular those of magnesium on the cardiovascular system are believed to
reflect the current exposure which means that a couple of monts are sufficient
for „adaptation“ to a new source of water with low content of magnesium and/or
calcium. Adaptation here does not mean adaptation of the organism to the water
of an inadequate composition but time within which the intake of drinking water
of inadequate composition may manifest itself by a disorder of consumer’s health
(Rubenowitz et al, 2000). Illustrative are cases among Czech and Slovak
population who started to use reverse osmosis-based systems for final treatment
of drinking water at their home outlets in 2000-2002 and several weeks later
reported different health complaints suggestive of acute magnesium
deficiency.New knowledge of protective effects of drinking water calcium and
magnesiumCalcium alone probably has a positive protective effect against some
neurological disturbances in the elderly as evidenced by a French case study.
The results in a region supplied with drinking water containing Ca > 75 mg/l
were by 20% more favourable compared to a drinking water Ca level < 75 mg/l
(Jacqmin et al, 1994). A Mallorca study reported that children in the areas
supplied with drinking water containing higher calcium levels showed
statistically significantly lower incidence of fractures compared to those
supplied with water poorer in calcium, if drinking water fluorides and
socio-economic conditions were taken into account (Verd Vallespir et al,
1992).While in males no study evidenced that the water calcium level could have
an effect on the risk for death from myocardial infarction, in females a low
water calcium level proved to be one of the risk factors in this regard
(Rubenowitz et al, 1999). Reality of such relationship is supported by the known
fact that calcium deficiency may cause hypertension. Meta-analysis of several
studies including almost 40 thousand population showed an inverse correlation
between the calcium intake from food and blood pressure (Capuccio et al, 1995).
Moreover, several mechanisms are known by which the calcium implication in blood
pressure fall can be explained (Rubenowitz et al, 1999).An inverse correlation
between the calcium intake with food and blood pressure was also described in
pregnant women in whom calcium supplementation is effective in blood pressure
reduction. Higher intake of calcium is believed to decrease smooth muscle
contractility and tonus, which clinically results in lower blood pressure and
lower rate of pre-term births. In this light, an epidemiological combined
ecologic case-control study was carried out in Taiwan in 1781 females:
relationship between the drinking water calcium level and birth weight of first
borns was analyzed. Drinking water calcium was found to be a beneficial
protective factor statistically significantly reducing the risk for pre-term
birth and low birth weight (Yang et al, 2002).An inverse correlation between the
intake of an element with food and blood pressure wasconfirmed in most studies
also for magnesium (Mizushima et al, 1998).A low magnesium content of drinking
water was found to be a risk factor for motor neuron disease (Iwami et al, 1994)